Ments



Patented :Ndv'. a9,- 1932 temperature of the reaction, within thecatalytic mass, due to the. reaction being highly een gen from steamand. a hydrocarbon the presence of a catalyst there has been consid-':romt s. nnnxnnx, or crrannns'roi'n-wnsr mags, so a. LDU ron'r Ian-moonsa conrona'rron or DELAWARE:

No Drawing.

This invention relates to a process for the manufacture of hydrogen bythe interaction of a hydrocarbon with steam int-heprescnce of a catalystand' particularly to eifectingsuch areaction in a plurality of catalyticreaction stages. i

In the; commercial manufacture of hydroerable di-fiiculty encounteredinsustaining the.

ndothermic.- Various expedientshave suggested, therefore, to supply thenecessary heat tothe reaction;- For instance; it has been proposedto'employ electrical heating within the catalyst bed, external heatingofthe catalyst chamber, the injection of oxygen into the gas during the--reaction, thereby supplying the needed heat by partial combustion ofthereacting gases, and many other processes. The proposed methods,however for temperatureand at the same time require but simple apparatusin which to effect it.

sustaining the temperature of the reaction,

which are for use in single stage processes, do notafiord' ease ofcontrolling the reaction An object of the present invention is to rovidea process for thepreparation of hy o-f. gen by the'interaction of a 'hdrocarbon and steam in the presence of a cata yst. A further object ofthis invention is to provide a process for aifording accurate cont-rolofthe temper-- ature of the reaction. A still-further object 1' of theinvention is to provide-a. process in which a hydrocarbonis convertedinto'h'ydro: gen by means of a plurality of catalytic reac-' tions'tages. Other objects will hereinafter ac' ion, and particular gnconducting the hydrocarbon-steam rewhen conducti it at temperaturesbelow. 00. C., I have found that in order to obtain efiicientconversionin a single deep catalyst bed, ,of the usual type, it isnecessary to heat the gases jprionto their admission "thereto to atemperature much higher than the .o timum conversion temperature. Forexam e,- anexcellentcon versionztemprature, w en: using a nickelcatalyst promoted with aluminum oxide,

ture for the conversion. As would be e vmemm, assrenong Br msnnassreisra comma; or-wrnume'rou, nnnawann,

PROCESS Brfin ummcrnar: or mn emr '4pp at 6a filed 8. 19:30.- stra -t,494,249.-

approximately I 525 -0." To eifect. substantially complete conversion insuch a catalytic mass in -'a single converter, inlet temperature of thegas proximately 8252' (3.. and with even as high the necessary ture willbe well belowthe optimum temperaxpect" ed,-' a rapiddet'erioration andloss of activity of-the expensive catalytic mass, particularly thatportion with which the gases'initially contact, results. I'have'fouhdthat these disshould be apan inlet temperature as. this, the exitteinperaadvantages can-be overcome by. effecting the reaction in aplurality of catalytic reaction stages while supplying tot-he gasesbetween thestages the quantity of heat lost in the precedmg'tstagejprior to their admission mto the succeeding stage, Furthermore, if thespace velocity of the gases in each sta e be so regulated-that it isproportional to t e'rate of reaction in" that "stage accuratetemperature control of the catalysis and the progress of the reactioncan be maintained. By this proc- Y ess the gases remain in contactwith-the catalyst in each stage a lengthoftime governed substantially bythe composition'of the gases, whereby efficient conversion in eachconversion chamber and an accurate control of the temperature of thewhole reaction are obtained while thetemperature drop through eachconerter can. be held within proper VYhen preparindgrliydrogen'by-myprocess, the mixture of hy ocarbon and steam is generally preheated to apredetermined temperature which is suflicient to give an averageopt-imum temperature of the gases 1n the first conversion stage;The'gases prior to their admission into the first conversion stage are's'o'far from equilibrium that when they contact with the catalystQajrapid reaction is set up with a'resultant rapidlossfin temperature.

With each subsequent stageof the reaction,"

assuming equivalent itemperature and other operating. conditions in eachstage, the gases are. successively closer to equilibr um with 'a resultthat thelreaction velocity inthe' latter stage's'generally successivelydecreases. By controlling the space velocity in a manner whichsubstantially proportional to there-- by my invention. A-lth asDuetothemdothenniemtumofthe athatthegasesmust .BLEST CORY- have that'eflieiait conversion can be efieded in anystagenomatber'whatflneveloeityofthem- .acfiombeinthats fltl'ythedisadvantages offlnehighreadionntem- I sulfing in a raidloss'in and,ultimatelyin m-w ofconversion andthe disadvantages oflowpercentageconversion at the lower temperatures am y ofl'set cated, the reactionrate generally fibmthefimttothe'lastshggthisisnotnecesarily txfle "1xnler all conditions of opera,-

- tion,forbyem'ployingalowtem do!" L ingthefigsbstagesofthereadion andincteasing the tem of the conversion dunEggthelatterdagestheefi'ectofthe o thegaeestocquilibriumislessmarkedsothat the velocities may even :5 Inanyevent y v e p g y ep y m e gfaiifif m van 0 o inwvenlionwilllzaexealnzzerl hydrocn bon-siczmleadion, theteam tmedmpheadnfihgeoftheconversiomalregulation of the space velocity,is v be heated prior to their en thenext conversionehge. Thisinof thegasm between convelsion operahmscanbecan'iedoutby pwiingthem uprefetably snitableheatex out'ofdilectcmtaetwiththefluii'Byaconelafion'oftheheat added, u-iortn fl1e.fi1st lage andbetwemtheentperhuedmpthtougheaehdagecanbeeig fcctech to-theoperahm of my invention,neverflxe- 1% 1t afiords'an 'aculrate contmol'oi the condlhmsof'Inozdertolealimflaeultimateufiiityof 45 lgYdtishotmaterialM m stagesempoyed, althou' ve mmdthat usm' g thxeestagesanexcellmtworkinglnl cecanhe betweenthecostoftheappamhns and advantagesofusingaplmalityofWhmus'ingsomecata; lyshghowevugitmaypmve of-aflvantagetnuseagreatu-orlesseennmberofstagm.

sscatalyhcreacfionwhichfecdintothe codezhgamtheamountofheatlmtinflaepmccdlngstage,mayheofan saitablet owingtotheee'seof'heatasareavailahlewhmmulheatersav'ailnhle, for 1H9 convertexs ves tompplyheattothe mlimitedduetoex'aet ion I H] An wll as above indicarbo'lvstandtakingintocomidemficntheleacfionnteinthepalfimlarshgeasiell asoflaetconditions o -mnm ionwha togzsntio, temperature, pressum,

It willbelmdetstoodthattlmeuenymerousvaliations which mybw p y g momfully a quaint the expertin thk art withapl'adicel application of my inwillnotinanyyaylimititxseopebythe Specificdetails of tezqpeqhne,

Afterdryingatm eirmo'muxm tmnperatzlmintowg rbsofaboilingm,.timoinichrlnitzatezfiputsof, cuinmnitmtgallofwlfidlmldhefiee fro]! In.HR. Illa. M npoismxs,in7oilaltsofdisfilledialum.- Aimhit, a m is mpldgm \"Hnm momma-mow .until I uetigla I 135 of memmmae em nm-m l.- ecfwaforcnehoiar, Agasemsihixtme 32G lo volqme's ofsteam per volume.ofispaseflthmughflle Plane eerisofsmple' cm- .reaction rate is met withunder these conditions of operation. By thus regulating the spacevelocity in each converter, a substantially equal temperature drop isobtained in each. The gases are preheated prior to entering the firstconverter to a temperature of approximately 650 G.,--at the exit of thisconverter the temperature will have dropped to approximately 525 C. Theheat of the gases is increased again to 650 C. by external heat exchangewith any suitable type of heater and the cycle repeated to the lastconverter.

There are many advantages realized by effecting a substantially equaltemperature drop through each conversion stage. For instance, thecatalytic mass in each is maintained at its optimum working temperature,thus giving long catalyst life with high conversion and as the length oflife of each catalyst bed is approximately the same, the operations arenot intermittently interrupted by the necessity of replenishing anexhausted catalyst in one of the converters.

Various changes may be made in the above process for the preparation ofhydrogen from the hydrocarbons and particularly those of the paraiiinseries as well as in the catalyst, space velocity, steam to gas ratio,and other factors employed, providing a plurality of converters be usedwith external heaters between the converters, and, iffilesired', thespace velocity in each be varied in proportion to the reaction, ratetherein, without departing from the invention or sacrificing any of theadvantages that may be derived therefrom. I claim: 1.'A process forthe'preparation of hydrogen by the interaction of steam and a gaseoushydrocarbon which comprises conducting the conversion of the hydrocarbonin a plurality of separate catalytic reaction stages, the space velocityin each stage being substantially proportional to the reaction rate .inthat stage.

2. A process for the preparation of hydrogen by the interaction of steamand a gaseous hydrocarbon which compfises'conducting the conversion ofthe hydrocarbon in a plurality of separate catalytic reaction stages,the space velocity in each stage being substantially proportional tothe'reaction rate in that stage; the quantity of heat lost in each stagebeing added to the gases prior to their entryinto the succeeding stage.

. 3. Aprocess for the preparation'of hydrogen by, the interaction ofsteam and a gaseous hydrocarbon which comprises conducting theconversion of the hydrocarbon in three catalytic reaction stages, thespace velocity in each stage being substantially proportional to thereaction rate in that stage.

4. A process for the preparation of hydrogen by the interaction of steamand a gaseous hydrocarbon which comprises conducting the conversion ofthe hydrocarbon in three cataperature drop thru each stage beingsubstantially equal.

6. A process for the preparation of hydrogen by the interaction of steamand a gaseous hydrocarbon which comprises conducting the conversion ofthe hydrocarbon in three catalytic reaction stages, the hydrocarbon andsteam entering each stage at a temperature of approximately 650 C. --andleaving each stage at a temperature of approximately 525 C.

7 The process for the preparation of hy- I drogen by the interaction ofsteam and methane which comprises conducting the conversion of themethane in a plurality of catalytic reaction stages, heat being added tothe gases between the stages by external heat exchange, the heat addedbetween the stages being substantially equal.

-8. A process for the preparation of hydrogen by the interaction ofsteam and a gaseous hydrocarbon which comprises conducting theconversion of the hydrocarbon in a plurality of separate catalyticreaction stages, the space velocity decreasing proportionately from thefirst to the last stage. r

In testimony whereof, I aflix my signature.

JOHN S. BEEKLEY.

